WO2007100811A2 - nanotubes de platine et d'alliage à base de platine comme électrocatalyseurs pour piles à combustible - Google Patents

nanotubes de platine et d'alliage à base de platine comme électrocatalyseurs pour piles à combustible Download PDF

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WO2007100811A2
WO2007100811A2 PCT/US2007/005053 US2007005053W WO2007100811A2 WO 2007100811 A2 WO2007100811 A2 WO 2007100811A2 US 2007005053 W US2007005053 W US 2007005053W WO 2007100811 A2 WO2007100811 A2 WO 2007100811A2
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platinum
nanotubes
catalysts
catalyst
based alloy
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PCT/US2007/005053
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WO2007100811A3 (fr
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Yushan Yan
Zhongwei Chen
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The Regents Of The University Of California
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Priority to JP2008556475A priority Critical patent/JP5580990B2/ja
Priority to US12/224,197 priority patent/US9214680B2/en
Priority to EP07751787.8A priority patent/EP2008322B1/fr
Publication of WO2007100811A2 publication Critical patent/WO2007100811A2/fr
Publication of WO2007100811A3 publication Critical patent/WO2007100811A3/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/04—Alloys based on a platinum group metal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8803—Supports for the deposition of the catalytic active composition
    • H01M4/8814—Temporary supports, e.g. decal
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/928—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • MCA proton exchange membrane fuel cells
  • DMFC direct methanol fuel cells
  • Pt platinum
  • PtPb platinum-palladium
  • the present invention includes, but is not limited to, improved cathodic catalysts formed from such platinum nanotubes (PtNTs) and platinum-palladium nanotubes (PtPdNTs).
  • a fuel cell is a device that converts the chemical energy of a fuel and an oxidant directly into electricity without combustion.
  • the principal components of a fuel cell include electrodes catalytically activated for the fuel (anode) and the oxidant (cathode), and an electrolyte to conduct ions between the two electrodes, thereby producing electricity.
  • the fuel typically is hydrogen or methanol
  • the oxidant typically is oxygen or air.
  • Fuel cells are electrochemical devices that convert chemical energy directly into electrical energy. Compared with internal combustion engines, fuel cells are not limited by the Carnot cycle and in principle could have higher efficiency. With pure hydrogen as the fuel, fuel cells are very environmentally friendly. The combination of high efficiency, low environmental impact, and high power density has been and will continue to be the driving force for vigorous research in this area for a wide variety of applications such as transportation, residential power generation, and portable electronic applications. For portable electronic applications, important features include high power density (i.e., longer battery life) and compactness.
  • Electrodes for fuel cells which typically includes spraying and/or brushing of platinum supported on carbon powder, is incompatible with microfabrication techniques. Therefore, there is need for improved electrodes and methods of preparing such electrodes for PEMFCs and DMFCs.
  • Direct methanol fuel cells have attracted enormous attention as a promising power source for portable electronics applications such as laptop computers and cell phones.
  • the interest in commercializing DMFCs is in part due to the fuel cell's simple system design, high energy density and the relative ease with which methanol may be transported and stored, as compared with hydrogen.
  • platinum supported on a carbon substrate is configured in the cathode as a catalyst for activating the oxygen reduction reaction (ORR).
  • ORR oxygen reduction reaction
  • a platinum-ruthenium alloy is usually used as the anode electrocatalyst, and may be supported on a carbon substrate.
  • the electrolyte is usually a perfluorosulfonate membrane, for which NAFION (available from DuPont) is a commonly utilized commercially available membrane.
  • NAFION available from DuPont
  • One of the major problems encountered in DMFCs is methanol crossover from the anode to the cathode. The permeated methanol causes "poisoning" of the cathode platinum catalyst and depolarization losses due to the simultaneous oxygen reduction and methanol oxidation on the platinum catalyst.
  • the rotating disk electrode (FIG. 28), which is used in the testing of the present invention as described below.
  • the rotating disk electrode (RDE) consists of a disk on the end of an insulated shaft that is rotated at a controlled angular velocity. Providing the flow is laminar over all of the disk, the mathematical description of the flow is surprisingly simple, with the solution velocity towards the disk being a function of the distance from the surface, but independent of the radial position.
  • the rotating disk electrode is used for studying electrochemical kinetics under conditions, such as those of testing the present invention, when the electrochemical electron transfer process is a limiting step rather than the diffusion process.
  • PEMFC proton exchange membrane fuel cells
  • DMFC direct methanol fuel cells
  • Their successful commercialization is, however, very much dependent on the activity and durability of their electrocatalysts.
  • all pre-commercial low temperature fuel cells use supported Pt and Pt alloys as their electrocatalysts.
  • the critical properties to consider when choosing an electrocatalyst support include its electrical conductivity, surface area, macro-morphology, microstructure, corrosion resistance, and cost.
  • Carbon black such as Vulcan XC-72
  • Vulcan XC-72 has been the most widely used electrocatalyst support because of its reasonable balance among electronic conductivity, surface area, and cost.
  • nanostructured carbon materials with graphitic structure such as nanotubes (CNTs), nanofibers (CNF) nanocoils, nanoarrays and nanoporous hollow spheres.
  • CNTs are of particular interest due to their unique electronic and micro and macro structural characteristics.
  • CNTs have also been shown to be more corrosion-resistant than CB under simulated fuel cell operation conditions.
  • DMFCs have been attracting great attention for powering small devices, such as laptop computers, cell phones, and personal digital assistants, because of their high energy density, ease of handling liquid fuel, and low operating temperature.
  • the slow electrokinetics of the anode reaction - a methanol oxidation reaction - is still a key problem to the commercialization of DMFCs.
  • expensive noble metal alloys typically Pt-Ru, with a high electrode metal loading (e.g. 5 > 2.0 mg/cm 2 ) are employed in order to offer a reasonable fuel cell performance (e.g., 80 mW/cm 2 at cell temperature of 90 0 C and O 2 pressure of two atmospheres).
  • SWNTs single-walled carbon nanotubes
  • MWNTs multi- walled carbon nanotubes
  • DWNTs double-walled carbon nanotubes
  • SWNTs can have a large surface area (e.g., 500-1000 m 2 /g) due to their small diameter (e.g., one nm), which is a favorable property as catalysts support.
  • they normally contain a significant amount (e.g., two-thirds) of semiconducting tubes, which are poor electron conductors and thus are expected to be a poor electrocatalytic support.
  • MWNTs are highly conducting, but they have limited surface area (e.g., 100-200 m 2 /g) due to their large diameter (e.g., forty nm). It was recently shown that most DWNTs are conducting tubes and that they can have high surface areas (e.g., 500-1000 m 2 /g). Thus a natural and logical choice for an electrocatalyst support is DWNTs.
  • the slow rate of the oxygen reduction reaction (ORR) in the polymer electrolyte membrane fuel cell (PEMFC) is the main limitation for automotive applications. It has been shown that the Pt 3 Ni(111) is 10-fold more active for the ORR than the corresponding Pt(11 1) surface and 90-fold more active than the current state-of-the-art Pt/C catalysts for PEMFC.
  • the Pt3Ni(l 11) surface has an unusual electronic structure (d-band center position) and arrangement of surface atoms in the near-surface region. Under operating conditions relevant to fuel cells, its near-surface layer exhibits a highly structured compositional oscillation in the outermost and third layers are Pt rich and the second atomic layer is Ni rich. The weak interaction between the Pt surface atoms and non- reactive oxygenated species increases the number of active sites for O 2 adsorption.
  • PEFCs polymer electrolyte fuel cells
  • a new class of low-cost (non-precious metal)/(heteroatomic polymer) nanocomposite catalysts for the PEFC cathode capable of combining high oxygen- reduction activity with good performance durability.
  • PEFCs operate with a polymer electrolyte membrane that separates the fuel (hydrogen) from the oxidant (air or oxygen).
  • Precious-metal catalysts predominantly platinum (Pt) supported on carbon, are used for both the oxidation of the fuel and reduction of the oxygen in a typical temperature range of 80-100 0 C.
  • Pt platinum
  • PEFCs suffer from insufficient performance durability, arising mainly from cathode catalyst oxidation, catalyst migration, loss of electrode active surface area, and corrosion of the carbon support.
  • PEFCs In a direct methanol fuel cell (DMFC), the Pt cathode also endures a performance loss resulting from the lack of tolerance to methanol diffusing through the membrane from the anode side of the cell.
  • DMFCs direct methanol fuel cell
  • the Pt cathode also endures a performance loss resulting from the lack of tolerance to methanol diffusing through the membrane from the anode side of the cell.
  • PEFCs are in need of efficient, durable and, most importantly, inexpensive catalysts, as alternatives to Pt and Pt-based materials.
  • the Pt catalyst should be replaced at both fuel- cell electrodes, the substitution of the cathode catalyst with a non-precious material is likely to result in significantly greater reduction of Pt needed for PEFCs. This is because the slow oxygen reduction reaction (ORR) at the cathode requires much more Pt catalyst than the very fast hydrogen oxidation at the anode.
  • ORR oxygen reduction reaction
  • Fuel cells are expected to become a major source of clean energy with particularly important applications in transportation.
  • existing fuel-cell technology still has drawbacks, including the instability of the platinum electrocatalyst for the ORR at the cathode.
  • Recent work recorded a substantial loss of the Pt surface area over time in proton-exchange membrane fuel cells (PEMFCs) during the stop-and-go driving of an electric car; this depletion exceeded the Pt dissolution rates observed upon holding at constant potentials for extended time spans.
  • PEMFCs proton-exchange membrane fuel cells
  • the present invention is directed to catalysts, electrodes and membrane electrode assemblies suitable for use in proton exchange membrane fuel cells (PEMFC -
  • Fuel cells bring the promise of clean electrical energy generation with high efficiency.
  • the polymer electrolyte fuel cell operating at relatively low temperature (typically from -20 to 140° C.) with hydrogen (proton exchange membrane fuel cell, PEMFC) and liquid methanol feed (direct methanol fuel cell, DMFC) is particularly promising for portable power, back-up power, motive power, and stationary power generation.
  • PEMFC proton exchange membrane fuel cell
  • PEMFC proton exchange membrane fuel cell
  • PEMFC proton exchange membrane fuel cell
  • direct methanol fuel cells
  • the present invention provides a proton exchange membrane fuel cell with nanostructured components, in particular, the electrodes.
  • the nanostructured fuel cell has a higher precious metal utilization rate at the electrodes, higher power density (kW/volume and kW/mass), and lower cost.
  • the nanostructured fuel cells are not only attractive for stationary and mobile applications, but also for use as a compact power supply for microelectronics such as laptops, cell phones and other electronic gadgets.
  • aligned (oriented) arrays of platinum and platinum alloy nanotubes are used for forming electrocatalysts. Electrocatalyst durability has been recently recognized as one of the most important issues that have to be addressed before the commercialization of the proton exchange membrane fuel cells (PEMFCs).
  • the common catalyst used in proton exchange membrane fuel cells incorporates carbon black as a support structure (Ptjjlll).
  • carbon black does not provide sufficient simultaneous access of gas, proton, and electron.
  • membrane electrode assemblies (MEA) using carbon black provide low platinum utilization (20-30%), a dense catalyst layer, low catalyst activity and are difficult mass transport.
  • the present invention is directed to a new class of cathode catalysts based on supportless platinum nanotubes (PtNTs) and platinum alloy nanotubes, for example, platinum-palladium nanotubes (PtPdNTs), that have remarkable durability and high catalytic activity. Due to their unique combination of dimensions at multiple length scales, the platinum nanotubes of the present invention can provide high platinum surface area due to their nanometer-sized wall thickness, and have the potential to eliminate or alleviate most of the degradation pathways of the commercial carbon supported platinum catalyst (Pt/C) and unsupported platinum -black (PtB) as a result of their micrometer-sized length.
  • PtNTs platinum nanotubes
  • PtPdNTs platinum-palladium nanotubes
  • the platinum nanotube catalysts of the present invention asymptotically approach a maximum of about twenty percent platinum surface area loss in durability test, while the commercial PtB and Pt/C catalysts lose about fifty-one percent and ninety percent of their initial surface area, respectively. Moreover, the PtNT and PtPdNT catalysts of the present invention show higher mass activity and much higher specific activity than commercial Pt/C and PtB catalysts.
  • the present invention includes the production of platinum and platinum based alloy nanotubes (5 to 100 nm diameter, 0.1 to 100 ⁇ m long and 1-10 nm wall thickness) as catalysts for PEMFC and DMFC that have the following advantages compared with conventional catalysts:
  • Tubular morphology of Pt and Pt based alloy nanotubes enhances charge and mass transportation in the electrodes.
  • the synthesis of platinum and platinum based alloy nanotubes may be achieved using silver nanowires.
  • the process of the present invention includes a galvanic displacement reaction that occurs as a solution containing a platinum precursor is in contact with a silver nanowire.
  • the elemental platinum should be mainly confined to the vicinity of the template surface. Once the concentration of platinum atoms has reached a critical value, they will nucleate and grow into small cluster, and eventually evolve into a shell-like structure around the template (a silver nanowire). This reaction is believed to initiate on the facets with the highest surface energy and then proceed to those with lower energies.
  • the thin shell formed in the early stage is incomplete, and thus it is possible for Pt(II) and Ag(I) ion to diffuse across this layer until the template has been completely consumed.
  • the silver is oxidized and the platinum produced has a 2:1 ratio, which leads to a gap between the platinum tube and the shrinking silver wire.
  • transport of mass from the side of the tube is also possible.
  • the openings in the wall of the platinum shell will be closed to form a seamless platinum shell.
  • the synthesis of platinum and platinum based alloy nanotubes may be achieved using selenium nanowires.
  • the process of the present invention includes conformal coating of selenium templates with platinum and may occur via two distinct reduction reactions: (i) the initial reduction of the Pt(II) salt by a selenium template at the Pt-Se interface, and (ii) the reduction of the Pt(II) salt by an alcohol solvent.
  • the synthesis of platinum and platinum based alloy nanotubes may also be achieved by a surfactant method of the present invention.
  • the rodlike micelles of Ci 2 EOg molecules in an aqueous medium are combined with much larger-sized sorbitan-based non-ionic surfactant molecules to form an aqueous solution of the mixed surfactant cylindrical micelles.
  • the mixed micellar solution may be converted into a hexagonal LC.
  • the platinum species confined to the aqueous region of the molecular assemblies are reduced into platinum atoms so as to form the nanotubes.
  • FIGURE 1 depicts a schematic diagram of a membrane electrode assembly for a proton exchange membrane fuel cell.
  • FIG. 2 depicts a schematic of a membrane electrode assembly for a direct methanol fuel cell.
  • FIG. 3 is a typical fuel cell (H2) polarization curve.
  • FIG. 4 is a schematic diagram of a catalyst having platinum disposed on carbon black and NAFION polymer electrolyte.
  • FIG. 5 is a schematic of a platinum nanotube.
  • FIG. 6 depicts a graph of the theoretical surface area of a platinum nanotube versus the wall thickness of the platinum nanotube.
  • FIG. 7 depicts a graph of the theoretical catalyst layer thickness versus the outside diameter of a platinum nanotube, assuming close-packed platinum nanotubes.
  • FIG. 8 is a schematic of a method for formation of a platinum nanotube from a silver nanowire according to the present invention.
  • FIG. 9 is a schematic of a method for formation of a platinum nanotube from a selenium nanowire according to the present invention.
  • FIG. 10 is a schematic of a method for formation of a platinum nanotube using a surfactant method according to the present invention.
  • FIG. 11 is a schematic representation of platinum or platinum based alloy material transfer system aligned vertically on a substrate.
  • FIG. 12 is a SEM image showing the diameter of silver nanowires.
  • FIG. 13 is a TEM image and an electron diffraction pattern (inset) showing the diameter of silver nanowires (AgNWs).
  • FIG. 14 is a SEM image showing the length of silver nanowires.
  • FIG. 15 is a SEM image showing the diameter of platinum nanotubes made from silver nanowires according to the present invention.
  • FIG. 16 is a TEM image and an electron diffraction pattern (inset) showing the diameter of a platinum nanotube made from a silver nanowire according to the present invention.
  • FIG. 17 is a SEM image showing the length of platinum nanotubes made from silver nanowires according to the present invention.
  • FIG. 18 is a graphical representation of X-ray diffraction (XRD) patterns of Pt/C,
  • PtB 3 PtNTs and PtPdNTs.
  • FIG. 19 is a SEM image showing the length of selenium nanowires.
  • FIG. 20 is a TEM image showing the diameter of selenium nanowires.
  • FIG. 21 is a SEM image showing the diameter of platinum nanotubes formed from selenium nanowires according to the present invention.
  • FIG. 22 are graphical representations of Cyclic voltammetry (CV) curves versus cycle numbers for (A) Pt/C, (B) PtB and (C) PtNTs.
  • FIG. 23 is a schematic diagram of normalized electrochemical surface area (ECSA) as a function of the cyclic voltammetry (CV) cycle number obtained for platinum on carbon (Pt/C), commercial platinum-black and platinum nanotubes (PtNTs) according to the present invention.
  • ECSA electrochemical surface area
  • CV cyclic voltammetry
  • FIG. 24 are TEM images of Pt/C (A) before, (B) after accelerated CV test; and of PtB (C) before, (D) after accelerated CV test; and of PtNTs (E) before, (F) after accelerated CV test.
  • FIG. 25 depicts oxidation reduction reaction (ORR) polarization curves for platinum on carbon (Pt/C), commercial platinum-black, platinum nanotubes (PtNTs) and platinum-palladium nanotubes (PtPdNTs)according to the present invention.
  • ORR oxidation reduction reaction
  • FIG. 26 is a SEM image of platinum-palladium nanotubes (PtPdNTs) made from silver nanowires according to the present invention.
  • FIG. 27 is a TEM image and an electron diffraction pattern (inset) of platinum- palladium nanotubes (PtPdNTs) made from silver nanowires according to the present invention.
  • FIG. 28 is a flow chart of the preparation protocol of catalyst dispersed GC disk electrode.
  • Electrocatalyst durability has been recently recognized as one of the most important issues that have to be addressed before the commercialization of the proton exchange membrane fuel cells (PEMFCs).
  • the durability problem is particularly severe in the cathode where the oxygen reduction reaction (ORR) occurs.
  • ORR oxygen reduction reaction
  • the most widely used cathode catalyst system is platinum (Pt) in the form of small nanoparticles two to five nanometers (nm) supported on amorphous carbon particle aggregates (Pt/C).
  • Pt/C platinum
  • the poor durability of the Pt/C catalyst is reflected by a fast and significant loss of platinum electrochemical surface area (ECSA) over time during fuel cell operation.
  • the carbon corrosion problem can be alleviated by the use of a more corrosion- resistant catalyst support, for example, graphitized carbons and carbon nanotubes. No effective solutions, however, exist for addressing the other three mechanisms.
  • the present invention provides a durable electrocatalyst by developing supportless platinum nanotubes (PtNTs) and platinum alloy nanotubes, for example, but is not limited to, platinum- palladium nanotubes (PtPdNTs) as the cathode catalyst. Due to their unique combination of dimensions at multiple length scales, PtNTs and PtPdNTs can provide high platinum surface area without the need of a high surface area support (for example, carbon black) by their nanometer-sized wall thickness (see FIGS. 5 and 6).
  • PtNTs and PtPdNTs can have the potential to eliminate or significantly reduce all of the four degradation pathways discussed above as a result of their micrometer-sized length.
  • PtNTs do not require a support, and thus the support corrosion problem is eliminated.
  • the micrometer-sized ( ⁇ m) length of the PtNTs (1-D nanostructure) makes the PtNTs less vulnerable, than the Pt nanoparticles (0-D nanostructure), to dissolution, the Ostwald ripening, and aggregation during the fuel cell operation.
  • the PtNTs and PtPdNTs like carbon nanotubes (CNTs), have an anisotropic morphology that can improve the mass transport and catalyst utilization.
  • a catalyst layer for example, cubic or hexagonal close-packing and vertically aligned on the Nafion membrane
  • they can also lead to a thin catalyst layer (for example, 0.5 ⁇ m at a PtNT wall thickness of two nanometers and a platinum loading of 0.2 mg/cm 2 ) (FIG. 7), further improving the mass transfer characteristics within the catalyst layer.
  • the present invention includes synthesized platinum nanotubes (PtNTs) and platinum-palladium alloy nanotubes (PtPdNTs) having about fifty nanometers in diameter and about five to twenty ⁇ m long, with about five to eight nanometer wall thickness.
  • the synthesized nanotubes were tested for their suitability as catalysts for ORR in PEMFCs.
  • PtNTs were synthesized by galvanic replacement reaction of silver (Ag) nanowires (AgNWs) developed by known methods.
  • the AgNWs were synthesized using a polyol method, and then refluxed with Pt(CHsCOO) 2 in an aqueous solution. After acid and heat treatment, the platinum nanotube product was collected by centrifugation.
  • a PEMFC 100 consists of an anode 110, a cathode 120, and a proton exchange membrane (PEM) 140.
  • the assembly of these three components is usually called a membrane electrode assembly (MEA).
  • MEA membrane electrode assembly
  • Hb pure hydrogen
  • O 2 oxygen
  • the protons 158 and electrons 154 produced in the anode are transported to the cathode through the proton exchange membrane and external conductive circuit having a load 150, respectively.
  • Water (H 2 O) is produced on the cathode as a result of the combination of protons and oxygen.
  • a hydrophobic diffusion layer consisting of carbon particles and polytetrafluoroethylene (PTFE) is usually used to manage the water content around the catalyst layer.
  • a direct methanol fuel cell 200 of the present invention includes an anode 210, cathode 220 and a polymer electrolyte membrane (PEM) 240 positioned between the anode and cathode.
  • a methanol (CH3OH) in water (H 2 O) solution is introduced at the anode, which releases carbon dioxide (CO 2 ) during methanol oxidation catalyzed by platinum (or other material) contained in the anode.
  • Air or oxygen (O 2 ) is introduced at the cathode, and water is formed during oxygen reduction (catalyzed by platinum or other material) as protons (H + ) move across the membrane.
  • a load 250 connected across the anode and cathode completes the electric circuit formed by electrons (e ⁇ ) released during methanol oxidation.
  • a fuel cell polarization curve (I- V) 310 has an uppermost horizontal theoretical curve 310 with certain associated loses in efficiency. For example, there is a significant cathode kinetic loss 320 and a somewhat smaller anode kinetic loss 350. In addition, there is an internal resistance loss 330 and a mass transport loss 340. PEMFCs also exhibit a significant cathode over-potential loss, while DMFCs exhibit significant anode over-potential loss.
  • the most commonly used electrode catalyst 400 is platinum 420, 425 supported on carbon fibers 410.
  • One of the challenges in the commercialization of PEMFCs and DMFCs is the high cost of noble metals used as catalyst (for example, platinum and its alloys). Decreasing the amount of platinum and its alloys used in a fuel cell electrode via the increase of the utilization efficiency of platinum has been one of the major concerns during the past decade.
  • the platinum should have simultaneous access to the gas, the electron-conducting medium, and the proton-conducting medium.
  • the simultaneous access of the platinum particle 420 by the electron-conducting medium and the proton-conducting medium is achieved via a skillful blending of platinum supporting carbon black particles 430 and the solubilized perfluorosulfonate ionomer (for example NAFION) 450.
  • the carbon particles conduct electrons and the perfluorosulfonate ionomer (for example, NAFION) conduct protons.
  • PEM proton exchange membrane
  • carbon nanotubes may be used to replace traditional carbon powders in PEMFCs and have been demonstrated by making membrane electrode assemblies (MEA) using carbon nanotube powders through a conventional ink process.
  • MEA membrane electrode assemblies
  • the use of carbon nanotubes and the resulting guaranteed electronic pathway eliminate the previously mentioned problem with conventional PEMFC strategies where the proton-conducting medium (e.g., NAFION) would isolate the carbon particles in the electrode layer. Eliminating the isolation of the carbon particles supporting the electrode layer improves the utilization rate of platinum.
  • the proton-conducting medium e.g., NAFION
  • the synthesis of platinum and platinum based alloy nanotubes may be achieved using silver nanowires.
  • the process of the present invention includes a galvanic displacement reaction that occurs as a solution containing a platinum precursor is in contact with a silver nanowire.
  • the elemental platinum should be mainly confined to the vicinity of the template surface. Once the concentration of platinum atoms has reached a critical value, they will nucleate and grow into small cluster, and eventually evolve into a shell-like structure around the template (a silver nanowire). This reaction is believed to initiate on the facets with the highest surface energy and then proceed to those with lower energies.
  • the thin shell formed in the early stage is incomplete, and thus it is possible for Pt(II) and Ag(I) ion to diffuse across this layer until the template has been completely consumed.
  • the platinum deposition goes on, the silver is oxidized and the platinum produced has a 2: 1 ratio, which leads to a gap between the platinum tube and the shrinking silver wire.
  • transport of mass from the side of the tube is also possible.
  • the openings in the wall of the platinum shell will be closed to form a seamless platinum shell.
  • the synthesis of platinum and platinum based alloy nanotubes may be achieved using selenium nanowires.
  • the process of the present invention includes conformal coating of selenium templates with platinum and may occur via two distinct reduction reactions: (i) the initial reduction of the Pt(II) salt by a selenium template at the Pt-Se interface, and (ii) the reduction of the Pt(II) salt by an alcohol solvent.
  • the synthesis of platinum and platinum based alloy nanotubes may also be achieved by a surfactant method of the present invention.
  • the rodlike micelles Of Ci 2 EO 9 molecules in an aqueous medium are combined with much larger-sized sorbitan-based non-ionic surfactant molecules to form an aqueous solution of the mixed surfactant cylindrical micelles.
  • the mixed micellar solution may be converted into a hexagonal LC.
  • the platinum species confined to the aqueous region of the molecular assemblies are reduced into platinum atoms so as to form the nanotubes.
  • the platinum or platinum based alloy nanotubes may be vertically aligned on a substrate as is known to one having ordinary skill in the art.
  • the diameter (FIGS. 12 and 13) and length (FIG. 14) of AgNWs are about forty nanometers and ten ⁇ m, respectively.
  • the electron diffraction pattern (FIG. 13 inset) shows the AgNWs have a multiple-twinned structure.
  • the diameter, wall thickness (FIGS. 15 and 16), and length (FIG. 17) of PtNTs are about forty nanometers, six nanometers and ten ⁇ m, respectively.
  • FIG. 16 inset indicates that the walls of the tubes are made of Pt nanocrystallites.
  • X-ray diffraction patterns (XRD) (FIG. 18) show that PtNTs and PtPdNTs have been formed successfully.
  • the face centered cubic (fee) lattice parameters of Pt/C, PtB and PtNTs and PtPdNTs are 0.3927, 0.3926, 0.3924 and 0.3897 nm, respectively.
  • the SEM and TEM depicting length and diameter for selenium nanowires are shown in FIGS. 19 and 20, respectively.
  • the TEM depicting the diameter of platinum nanotubes formed from selenium nanowires is shown in FIG. 21.
  • the degradation of an electrocatalyst can be evaluated by repeated cyclic voltammetry (CV) cycles with the proper lower and upper potential limits in an acid solution.
  • the durability tests were conducted by cycling the electrode potential between zero and 1.3 V vs. RHE at a scan rate of fifty mV/s in a N 2 purged 0.5 M H 2 SO 4 solution at 60° C.
  • the cyclic voltammograms for Pt/C (twenty weight percent platinum on Vulcan XC-72, ETEK), platinum black (PtB, ETEK) and PtNTs (FIG. 22) show a significant decrease of Pt ECSA for Pt/C and little reduction for PtNTs as the number of cycle increases.
  • the normalized ECSA as a function of the CV cycle number obtained for Pt/C and PtNTs is summarized in FIG. 23.
  • the Pt ECSA of PtNTs only decreases about 20% even after 1000 cycles while the RB and the Pt/C catalyst has lost about 51% and 90% of their Pt ECSA, respectively.
  • the Pt/C, PtB and PtNTs catalysts were examined by TEM after the CV cycling.
  • the platinum nanopart ⁇ cle size in the Pt/C catalyst increased from 2-5 nm to 10-20 nm (about 5 times increase) after the CV cycling (FIGS. 24A and 24B) confirming that the major cause for the platinum ECSA loss of Pt/C is by platinum nanoparticle ripening and possibly by aggregation due to carbon corrosion.
  • the particle size of PtB increased from five to ten nanometers to ten to twenty-five nanometers (FIGS. 24C and 24D) after CV cycling, which proves the platinum nanoparticle growth driven by surface energy minimization and Ostwald ripening.
  • FIG. 25 demonstrates typical ORR polarization curves of Pt/C and PtNTs obtained at room temperature in O2 saturated 0.5 M H2SO4 using a rotating disk electrode (RDE) at 1600 rpm.
  • the half-wave potentials of PtNTs, PtB and Pt/C are 837, 817 and 828 mV, respectively, showing that the activity of PtNTs is higher than that of the commercial PtB and Pt/C catalyst.
  • the insert in FIG. 25 shows their mass activity and specific activity that are better indicator of an electrocatalysts' quality.
  • PtNTs have a slightly higher mass activity, but significantly higher (3.8 times) specific activity than Pt/C at 0.85 V.
  • both the mass activity and specific activity of the PtNTs is higher (1.4 and 1.8 times, respectively) than that of the PtB.
  • the improved activity of PtNTs might be due to the preferential exposure of certain crystal facets of PtNTs.
  • the mass activity of PtNTs can be further improved by reducing the wall thickness of PtNTs and the use of Pt alloy nanotubes.
  • PtPdNTs were synthesized.
  • the SEM and TEM images show uniform diameters (45 nm), wall thickness (7 nm) and length (10 ⁇ m) of the PtPdNTs.
  • the inset of FIG. 27 shows an electron diffraction pattern of PtPdNTs.
  • the ORR curve shows the half-wave potential of the PtPdNTs is 851 mV, which is higher than that of PtNTs, PtB and Pt/C.
  • the mass activity of PtPdNTs is 1.4 and 2.1 times higher than Pt/C and PtB, and the specific activity of PtPdNTs is even 5.8 and 2.7 times higher than that of Pt/C and PtB electrocatalyst at 0.85 V.
  • the improved ORR kinetic of PtPdNTs compared to PtNTs could be due to change of bond distances which is shown in fee lattice parameters changes by the XRD results and also has been suggested in the literature.
  • PtPdNTs 5 which, due to their unique combination of dimensions. Specifically they have the potential to possess high surface area, high utilization, high activity and high durability.
  • Silver (Ag) nanowires were synthesized by reducing AgN ⁇ 3 (Aldrich, 99+%) with ethylene glycol (EG) (anhydrous, 99.8%, Fisher) in the presence of R seeds and poly(vinyl pyrrolidone) (Aldrich, Mw ⁇ 40,000) PVP.
  • EG ethylene glycol
  • PVP poly(vinyl pyrrolidone)
  • reaction mixture was diluted with acetone and centrifuged at 3000 rpm for fifteen minutes.
  • the supernatant containing silver particles could be easily removed using a pipet. This centrifugation procedure could be repeated several times until the supernatant became colorless.
  • Acid treatment was performed in 0.5 M HNO3 solution for two hours with stirring.
  • the PtNTs were separated by centrifuge with DDI H 2 O washing and ethanol.
  • the heat treatment was carried out under flow of Argon in an oven at 250° C. for 1 hour.
  • GC disk electrodes (5 mm diameter, 0.198 cm 2 , APE3T050GC, Pine Research Instrumentation) served as the substrate for the supported catalyst and were polished to a mirror finish (No.40-7218 Microcloth, Buehler). An aliquot of twenty ml catalyst suspension was pipetted onto the carbon substrate, leading to a metal loading of 40 ⁇ g me tai cm '2 for Pt/C, PtB, RNTs and PdPtNTs.
  • the cyclic voltammetry (CV) test for accelerated durability test is performed on the working electrode by cycling the voltage between 0 V to 1.3 V vs RHE in a Ar purged 0.5 M H2SO 4 solution at 60° C. The scan rate used was fifty mV/s. The electrochemical surface areas were calculated from the H2 desorption peak of the CV cycle. Totally one- thoudand cycles of CV are performed for each case. The area of adsorption or desorption of atomic hydrogen on the curve of the cyclic voltammogram has been frequently used to estimate the surface area of catalysts.
  • ECSA electrochemical active surface area
  • the electrode potential was cycled several times between 0 and 1.3 V in order to produce a clean electrode surface.
  • Current densities are normalized either to the geometric area of the glassy carbon substrate (0.198 cm 2 ) or the Pt surface area.
  • the scan rate used was five mV/s.
  • the measured current density,./ is described by the following relation:
  • TEM Transmission electron microscopy
  • SEM Scanning electron microscopy
  • XL30-FEG X-ray diffraction
  • XRD X-ray diffraction
  • Silver nanowires were synthesized by reducing AgN ⁇ 3 with ethylene glycol (EG) in the presence of Pt (or Ag) seeds and PVP.
  • EG ethylene glycol
  • Pt or Ag seeds and PVP.
  • 5 mL OfH 2 PtCl 6 solution (2XlO "4 M, in EG) was added to fifty mL of EG heated at 165° C. in a round- bottom flask (equipped with a condenser, thermo-controller, and magnetic stirring bar). After five minutes, twenty-five mL of AgNO solution (0.12 M, in EG) and fifty mL of PVP solution (0.36 M, in EG) were added dropwise (simultaneously) to the hot solution over a period of six minutes.
  • the reaction mixture was continued with heating at 165° C. for thirty to sixty minutes. Vigorous stirring was maintained throughout the entire process.
  • the product could be purified by centrifugation.
  • the reaction mixture was diluted with acetone and centrifuged at 3000 rpm for fifteen minutes. The supernatant containing silver particles could be easily removed using a pipette. The centrifugation procedure could be repeated several times until the supernatant became colorless.
  • annealing treatment and acid treatment are preferred.
  • the heat treatment is being done under flow of Argon in an oven at 350° C. for a certain time (for example, one to ten hours).
  • Acid treatment is performed in two to six M HNO 3 solution overnight with stirring.
  • the nanotubes can be separated by centrifuge with DDI H 2 O washing.
  • the solid selenium was formed in situ as spherical colloids by refluxing one- hundred mL selenious acid (0.05 M) with an excess amount of hydrazine (for example, ten mL of 0.6 M) at different temperatures (for example, 80° C, 90° C. or 100° C.) in a round- bottom flask for fifteen minutes. A brick-red color immediately appeared in the solution, indicating the formation of amorphous Se or a-Se that existed in the form of spherical colloids with sizes around 300 nm. Then the solution was diluted with three-hundred ml DDI H 2 O. The solution cooled to room temperature in thirty minutes.
  • the selenium nanowires (about one mmol) were dispersed with shaking in ten mL of ethanol hosted in a twenty mL scintillation vial. Platinum(II) chloride (2-10 mmol) was added. The vial was capped and heated at a temperature in the range of 40° C. to 70° C. under magnetic stirring until the desired thickness of Pt coating was achieved.
  • the Se-Pt nanostructures were isolated by filtration on track-etched polycarbonate membranes and rinsed twice with five mL of dilute HCl and twice with five mL of hot water (90° C).
  • Pt nanotubes were obtained by soaking the Se-Pt nanostructures in hydrazine for three to five hours and recovering them on TEFLON (polytetrafluoroethylene - PTFE) filters, followed by rinsing twice with five mL of ethanol. It was also possible to remove the Se cores by heating the dried samples on a hotplate at 200° C. to 250° C. for one to five minutes.
  • TEFLON polytetrafluoroethylene - PTFE
  • a similar procedure may be applied to form platinum based alloy nanotubes by using Au3+, Pt2+, Pd2+, Ir3+, Ru3+, Rh3+ and other metal salts solution as precursors.
  • the electrochemical characterizations of the catalysts were conducted in a thermostated (25° C.) three-compartment glass cell using Solartron electrochemical interface (SI1287). Electrode potentials were measured and reported against an Ag/ AgCI electrode placed close to the working electrode through Luggin capillary. A platinum wire was used as counter electrode.
  • the working electrode (rotating disk electrode) was prepared by applying catalyst ink to the glassy carbon disk (Pine Instrument, five mm diameter). The catalyst ink was produced by ultrasonically dispersing 4.0 mg catalyst in one mL ethanol for thirty minutes. Before each experiment the glassy carbon disk was polished to a mirror finish with 0.05 ⁇ m silica suspension, followed by ultrasonicating in acetone and DI water.

Abstract

La durabilité des électrocatalyseurs est reconnue depuis peu comme l'un des problèmes les plus importants qu'il faut régler avant la commercialisation des piles à combustible à membrane à échange de protons (PEMFC). La présente invention porte sur une nouvelle catégorie de catalyseurs à cathode à base de nanotubes de platine (PtNT) et de nanotubes d'alliage platine, par exemple, des nanotubes de platine palladium (PtPdNT) sans support, d'une durabilité remarquable et d'une activité catalytique élevée. Du fait de leur combinaison singulière de dimensions à de multiples échelles de longueur, les nanotubes de platine de la présente invention peuvent constituer une superficie de platine élevée grâce à leur épaisseur de paroi de l'ordre du nanomètre, et ont le potentiel de supprimer ou d'atténuer la plupart des circuits de dégradation du catalyseur de platine supporté par carbone commercial (Pt/C) et du noir platine non supporté (PtB) compte tenu de leur longueur de l'ordre du micron. Les catalyseurs à nanotubes de platine de la présente invention s'approchent de manière asymptotique d'un maximum d'environ vingt pour cent de perte de superficie de platine en test de durabilité, tandis que les catalyseurs commerciaux PtB et Pt/C perdent environ cinquante-et-un pour cent et quatre-vingt-dix pour cent de leur superficie initiale, respectivement. De plus, les catalyseurs PtNt et PtPdNT de la présente invention présente une activité de masse plus élevée et une activité spécifique beaucoup plus élevée que les catalyseurs commerciaux Pt/C et PtB.
PCT/US2007/005053 2006-02-24 2007-02-24 nanotubes de platine et d'alliage à base de platine comme électrocatalyseurs pour piles à combustible WO2007100811A2 (fr)

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US12/224,197 US9214680B2 (en) 2006-02-24 2007-02-24 Platinum and platinum based alloy nanotubes as electrocatalysts for fuel cells
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